Process for the preparation of polymers containing divalent hydantoin rings in their main chains

ABSTRACT

According to this invention, a polymer containing hydantoin rings is produced by a novel process comprising reacting (1-A) an aminoglycin derivative such as represented by the following formula:

United States Patent 1191 Iwata et al. I

Sept. 2, 1975 PROCESS FOR THE PREPARATION OF Inventors:

Assignee:

Filed:

Appl.

Kaoru lwata; Shigeyoshi Hara, both of I-Iino, Japan Teijin Ltd., Osaka, Japan Nov. 20, 1973 US. Cl 260/77.5 c; 117/1284; 260/309.5 Int. Cl C08g 22/00 Field of Search 260/77.5 c, 309.5

References Cited UNITED STATES PATENTS Primary ExaminerM. J. Welsh Attorney, Agent, or F irmSherman & Shalloway [57] ABSTRACT According to this invention, a polymer containing hydantoin rings is produced by a novel process comprising reacting (l-A) an aminoglycin derivative such as represented by the following formula:

H NRNHCH COOH (R is a divalent organic residue) with (2) a diaryl-carbonate; or (l-B) a polyglycine derivative such as represented by the following formula;

ROOCCH NHR-NHCH COOR (R is the same as the above, and R is hydrogen atom or a hydrocarbon residue) and (3) a primary diamine with (2) a diarylcarbonate. Thus, polymers containing hydantoin rings in their main chain, having thermal stability, can be obtained without using a poly-isocyanate as a starting reageut.

18 Claims, No Drawings PROCESS FOR THE PREPARATION OF POLYMERS CONTAINING DIVALENT HYDANTOIN RINGS IN THEIR MAIN CHAINS This invention relates to a process for the preparation of polymers containing in their main chains divalent hydantoin rings. More particularly, the invention relates to a process for the preparation of polymers containing in their main chains divalent hydantoin rings of the forin which R denotes hydrogen atom or a monovalent organic group, the ring being bonded with the main chain of a polymer through the bonds (1 and (3), or (2) and (3), and the remaining bond (2) or (1) not bonded with the main chain is bonded with hydrogen atom or a monovalent organic group. Some of such polymers containing divalent hydantoin rings in their main chains have been known for their wide utility such as the varnish for electric wire, because of their excellent heat stability, insulating property and relatively high solubility in polar solvent. (See, for example, US. Pat. Nos. 3,397,253, 3,448,170)

A typical known method of making such hydantoin ring-containing polymers can be illustrated, for example, by the formula below:

c cH

glycine derivatives with diisocyanate, or a masked didiphenylurethane derivatives polyfunctional compound which concurrently contains a functional group or groups easily reactable with isocyanate group, such as, for example, carboxyl group and/or hydroxyl group (-OH), can be used. According to the conventional method, therefore, usable types of isocyanates are severely limited, which in turn incur heavy limitations on the method for making hydantoin ring-containing polymers and the types of the products.

Accordingly, the object of the invention is to provide a novel process for making homoor co-polymers eonalone, but also an extremely wide variety of homoorco-polymers in which the organic groups are chainextended by an optional form of bond such as, for example, earbamide bond (-CONH-), carbimide bond carbester bond carbonate bond urea bond and urethane bond and the hydantoin rings, with relatively simple equipment.

Still many other objects and advantages of the invention will become apparent from the following more detailed description.

The foregoing objects and advantages of the invention are accomplishedby mutually reacting 1. polyfunctional glycine derivatives (I) containing at least one glycine residue (G), which are expressed by the formula) below,

A stands for an optional type of glycine residue (G) of the formula below; I

in which R is hydrogen atom or a monovalent organic group, and

X is a member of the group consisting of OR,

-SR, NHR' and N(R) (R standing for hydrogen atom or a monovalent organic group), the

residue being bonded with the organic group (Z) through either bond l or (2 the other bond bonding with hydrogen atom or a monovalent organic, and

B stands for at least one reactive group (B) selected from the group consisting of (B-l primary amino group (-NI-I.

(B-2) hydroxyl group (OH),

(B-3) earboxyl group or ester groups thereof of the formula, YOOC(Y standing for hydrogen atom or a monovalent hydrocarbon residue), and

(B-4) carboxylic anhydride group bonding with the two adjacent carbon atoms of the organic group (Z), and functional derivative groups thereof,

2. in at least the concurrent presence of a primary amino group-containing polyfunctional compound (II), if B in the above formula (I) denoting the polyfunctional glycine derivative stands for a reactive group other than primary amino group (B-l i.e., (8-2), or (8-4), the polyfunctional compound containing at least one functional group (F) reactable with the B (3-2, 8-3, or 3-4) as well as at least one primary amino group (-NH with 3. a diaryl carbonate (III) of the formula,

in which and (75 may be the same ordifferentpand each denotes a monovalent aromatic group, to

form

4. the polymers containing in their main chains the hydantoin ring groups of the formula (IV),

in which the definitions of R and the bonds (I), (2), and (3) are identical with those given as to the formula (IV) in the beginning.

As above-specified, according to the invention, when (i) the B is a reactive group other than primary amino group (B-l i.e.,

(8-2) hydroxyl group (OI-I),

(B-3) earboxyl group of the formula YOOC or an ester group thereof, (Y standing for hydrogen atom or a monovalent hydrocarbon residue) and/or (B-4) carboxylic anhydride group bonding with the two adjacent carbon atoms of the organic group (Z), and a functional derivative group thereof, at least the following three components,

a. the polyfunctional glycine derivatives (I), b. the primary amino group-containing polyfunctional compound (II), and c. the diary] carbonate (III) must be inter-reacted. However, when (H) the B in the formula (I) stands for primary amino group (NH only two of the above components, i.e., a. the polyfunctional glycine derivative (I) and c. the diaryl carbonate (III) need be mutually reacted, the presence of the primary amino groupcontaining polyfunctional compound (II) not being essential. (a+ Basically the reaction of the invention takes place among the gyleine residue (G), primary amino group (NH:), and the diaryl carbonate (III). to form the hydantoin ring'(IV) according to the reaction formula l below:

Reaction formula 1 R, 0 AH o l ll HNC C -N O A A A AX AH (G) (amino group) (III) I ll s cc til-N C N- +HX+OH +d OH in which R and the bonds l (2), and (3) have the same definitions as given previously, and the triangular marks denote the active sites, and the so formed hydantoin ring or ringsenter into the main chain of the polymer.

Thus, the concurrent presence of primary amino group (-NI-IQ with the glycine ire'sid ue .(G) and diary] carbonate (III) in the reaction systemof the invention is essential for the formation of hy dantoin ring or rings. When the polyfunctional glycine derivatives (I) contain both the glycine residue (G) and primary amino group (B-l therefore, it" is possible to form'hydantoin ringcontaining polymers through the reaction of the glycine I functional compound (II), polyfunctional glycine derivatives (I), and the diaryl-carbonate (III form ing the hydantoin ringas-well as advancing the polymerization reaction of the compound formed from the three.

-,The term, ;polyfunctional" is ,used in this ,speeification to denote thatthe compound possessesZto 6 functional groups, ie, the groups reactable under the reaction conditions of this invention, as indicated by the sum of (a-l-b) in, for example, the previously given formula (I), which is a positive integer of 2 to 6.

As the polyfunctional glycine derivatives component covered by the formula (I), particularly at least one polyfunctional glycine derivative selected from the following groups is used with preference:

(l-l) polyfunctional compounds each containing at least two glycine residues (G) (1-1 [in this case b equals zero in the formula (I), and a,-is a positive integer of 2to 6]; I (I-2) polyfunctional ;compounds each containing at least one glyycine residue (G) and at least one pri-' mary amino group (NH- in its molecule (I-2) [as to the formula I, A is the glycine residue (G),

and B denotes primary amino group (B-1 )1; and (I- 3) polyfunctional compoundseach containing at least one glycine residue (G) and at least onereactive group selected from the following: (a) hydroxyl group (-OH), V

' (b) carboxyl group or ester groupsthereof ex pressed by the formula YOQC (Y de'n'oting hy-' and functional derivative groups thereof, which is linked with the two adjacent carbon atoms of the organic group (Z). [in the case of (1-3 A in the formula (I) is the glycine residue (G); and B, a reactive group which may be (8-2), (8-3), or (8-4), but not primary amino group (Bl)]. &

Also as the primary amino group-containing polyfunctional compounds (II), at least one member of the following groups is preferred:, H

(II-l) polyamines each containingin'its.moleculeat least two primary amino groups(-, NH (II-2) aminohydroxyl compounds each, containing in its molecule at least onepromary amino group'and at least one hydroxyl gr o p O H;.) and (II-3) amino carboxylic acid derivatives each containing in its molecule at least one primary amino hydrocarbon resicoo group and at least one carboxyl group or an ester group thereof of the formula, I YOOC-(Y denoting hydrogen atom or a monovalent hydrocarbon residue) II-3). Hereinafter some of the preferred types of the subpr oc'ess will be explained.

- [TYPE I] The glycine residues covered the formula (G) can be divided into the following'two typtes, (Ga) and (Gb):

in which R is'a r -valent organicgroup,

R ','and1X have the same meanings-already'defined as -toformula (G), R; stands for hydrogen atom or a monovalent organic group, and r is a positive integer of 2' to 6. and

(l-lb) in which R, R, r, and X have the same meanings as in the above formulav (I- l a), and

R stands for hydrogen atom or a monovalent organic group. According tothe type 1 of this invention, at least one of the polyfunetional glycine derivatives of the above formula (I -1a or (I 1b)"is reacted with'at least one of the'polyarnines'of the formula (II-l (II-l) in which R is an S-valent organic. group,-and S is a positive integer of 2 to 6, and diary] carbonate of formula (III),

d O-CO' (III) in which d) and d) have the previously given definitions under heating, the mol number of the diary] carbonate being at least equal to r or S whichever is the lesser of the two. By this reaction the polymers containing divalent hydantoin ring groups of the formula,

T O R -c (IV-l) 0 II R, C

I c\ /N (I N C l, O

in which, R,, R and R have the previously given definitions can be obtained. v In the above reaction of type l belonging to the subject process, the mol number of the glycine residue (Ga) or (Gb) in the formula (l-la) or (l-lb) is made substantially equal to that of the primary amine in the polyamine of formula (ll-l and also the mol number of the diaryl carbonate (III) is made at least equal to that of the glycine residue (Ga) or (Gb) to effect the mutual reaction of the three components, i.c., polyfunctional glycine derivatives (I-la or l-l b), polyamine (ll-l and diaryl carbonate (lll), forming the aforespecificd hydantoin ring-containing polymers.

In the preferred embodiments, the r in the formula l-la or l-lb is a positive integer of 2 to 4, particularly 2. When the r is 3 or more, the product hydantoin ringcontaining polymers take reticulated or cross-linked structure, and when r is 2, substantially linear structure.

In the subject process of type l, the type l-l described below produces particularly favorable results.

[TYPE l-l} According to the type l-l, l. bis-glycine derivatives of the formula (1-4) or (1-5) below:

in which I R,, R and Xhave the already defined meanings as in which R,, R and X have the already defined meanings as to the formula (l-lb), and 5 R has the meaning as defined as to formula ([4),

2. diamine of the formula (ll-la) below,

z m .vllz in which R denotes a divalent organic group, and

.3. diaryl carbonate of the formula (III),

d O-CO' (Ill) in which d and 4: have the previously given definitions, are mutually reacted under heating, to form substantially linear hydantoin ring-containing polymers composed of the'r'ecurring structural units of the formula (IV-3) or (IV-4) below: 2

0 t R, R, 0 \C(|.--R R --'CC/ /\N Ru N/\ C C II II 0 0 0 0 (I! I R, R, C \C R BC/ \N R 9 \N i0 C--N -C ll l I ll 0 a u 0 which, R R R R and R have the previously given definitions.

In the above process of type (l-l as already mentioned, substantially equimolar quantities of the bisglycine derivatives of the formula (1-4) or (1-5) and the diamine of formula,(ll-la) are used, and the mol number of the diaryl carbonate (III) of at least twice that of the bis-glycine derivatives is used to produce the favorable results.

[TYPE 2] Another preferred type of the subject process can be described as type 2 below.

In the process of type 2, glycine derivatives of the formula (l-2a) or (l-2b) below,

of 1 plus m being a positive integer of 2 to 6, and X has the same meaning as defined as to formula (G),

O Od (III) in which (b and 1) have the previously given definitions, of the mol number at least equal to l or m whichever is the lesser of the two (Obviously, if 1 equals m, diary] carbanate of the mol number at least equal to either one is used) under heating, to form the polymers containing divalent hydantoin rings, in the main chains, which can be expressed by the formula (IV-l) or (IV-2) below:

\ (IV-l) 0 ll R, c (we) i A... O

which, R,, R and R have the alreadygiven definitions.

In the above type 2 process, both the glycine residue (Ga) or (Gb) and primary amino group (NH are contained in the polyfunctional glycine derivatives (l-2a) or (I-2b). Consequently the polymerization and the formation of hydantoin rings (IV-l) or (IV-2) progress, without the addition of primary amino groupcontaining polyfunctional compound (II).

In the above-described reaction, if I is greater than in, the product polymer contains residual glycine residue (Ga) or (Gb). Thus formed oligomer or polymer of suitable degree of polymerization may be put to the final use as it is or, if desired, the residual glycine residue (Ga) or (Gb) can be further converted into another form, or further reacted with the primary amino group-containing compound and diaryl carbonate (III) to form hydantoin rings.

Similarly, if m is greater than I, hydantoin ringcontaining polymers which also contain primary amino: groups are obtained, which can be used for the finally intended utility as it is, or may be further converted to other desired forms,

If m equals on the other hand, the glycine residue (Ga) of (Gb), and the primary amino group in the glycine derivative become substantially equimolar, and substantially all of those groups participate in the formation of hydantoin rings (IV-l or (IV-2) through the reaction with the diaryl carbonate (III). Obviously, it is also possible in the aforesaid cases of 111 or m l to cause all the glycine residues (Ga) or (Gb) and primary amino groups (NH present in the reaction system to participate in the hydantoin ring-forming reaction, by quantitatively adjusting the starting composition of the reaction system to make the glycine residues (Ga) or (Gb) and primary amino groups (-NH substantially equimolar.

The type 2 process as described above is a polymerization methodv characterized in that the polyfunctional glycine derivatives (I-2a) or (I-2b) contain both the glycine residue (Ga) or (Gb) and primary amino group (-NH in their molecules, and upon reaction with the diaryl carbonate (III), the glycine residues and primary amino groups form hydantoin rings while selfcondensing, and concurrently undergo polymerization. Such a method of making the hydantoin ringcontaining polymers is entirely impossible with the known methods employing isocyanates, because the isocyanate reacts with the amino or imino groups in the residues of glycine derivatives.

.It is also a conspicuous advantage common between the type 1 (including type 1-1) and type 2 (including later-described type 2-2) processes, that polymers of various degrees of polymerization ranging from oligomers to hydantoin ring-containing polymers of high degree of polymerization can be prepared with good control, by such procedures as, for example, adjusting the mol numbers of polyfunctional glycine derivatives and polyamine to be employed, or adjusting the ratio of r to S (type 1 process); or adjusting the ratio of I to m, or by further adding other polyamines or polyglycines, etc. (type 2 process): to regulate the ratio of total mol number of the glycine residues present in the reaction system to that of the primary amino groups. For example, the closer the total mol numbers of the glycine residue (Ga) or (Gb) and primary amino groups to each other, the higher becomes the degree of polymerization of the product. Conversely, the greater the difference between the two, the lower becomes the degree of pol- 4 ymerization.

Thus according to the subject process of types 1 and 2, hydantoin ring-containing polymers or oligomers of the desired degree 'of polymerization can be formed, which can be put to their final use as they are, or, if desired, can be further converted to the polymers of higher degrees of polymerization at any optional stage.

The type 2 process furthermore is practiced preferably with glycine derivatives (I-2a) or (I-2b) in which the sum ofI+ m is 2 to 4, particularly 2 or 3. lnter alia, when 1 equals 1 and m equals 1, such difunctional glycine derivatives, as reacted with the diaryl carbonate (III), form substantially linear hydantoin ringcontaining polymers while self-condensing, producing very advantageous results. Such a practice will be hereinafter explained as the type 2-2process.

[TYPE 2-2 In this type of practice according to the invention, the glycine derivatives of the formula (I6) or (1-7) below:

in which R R R9. and X have the significations given with respect to formula (1-4), or

N l R.

in which R,, R R and X have the significations given with respect to formula (1-5), is reacted under heating, with at least equimolar quanitity thereto of the diaryl carbonate of formula (III) below:

(lll

in which 4) and have the already given definitions, to form substantially linear hydantoin ring-containing polymers composed of the recurring structural units of the formula (IV-5) or (IV-6) below:

in which, R,, R R and R have the already given definitions.

The unique feature and advantages of the above type 2-2 process are as described as to the type 2 process.

[TYPE 31 Still another preferred practice of the subject process can be described as the process of type 3, in which:

1. the polyfunetional glycine derivatives (l-3a) or T, 0 -HNCC\/\ it X l in which R R R X, m, and l have the same significations according those given as to formula 1-221, and

B is at least one type of reactive moiety selected from the group consisting of a. hydroxyl group (OH), b. YOOC- (Y being hydrogen atom or a monovalent hydrocarbon residue), and c. carboxylic anhydride group bonded with the two adjacent carbon atoms of the organic group R or functional derivative groups thereof,

in which R R;,, R,,, X, m, and l have the same definition according defined as to formula (I-2b), and

B has the same definition as in the above formula (l-3a), is reacted with 2. at least one primary amino group-containing polyfunctional compound selected from the group consisting of (11-1) polyamine containing at least two primary amino groups (NH (ll-2) aminohydroxyl compound containing at least one primary amino group (NH and at least one hydroxyl group (-OH), and

(ll-3) aminocarboxylic acid derivatives containing at least one primary amino group (NH and at least one of the groups covered by the formula, YOOC-(Y being hydrogen atom or a monovalent hydrocarbon residue) and 3. diary] carbonate of the formula (III) below,

d O-2Od (Ill) in which (i: and may be same or different, and each denotes a monovalent aromatic group,

of the mol number at least equalling that of the glycine residue [1 in the foregoing formula (1-32.) or (I-3b) or that of the primary amino groups in the primary amino group-containing polyfunetional compound (ll-1, 11-2,

or "-3) whichever is the lesser of the two,

4. under heating, to form 5. the polymers containing in their main chains divalent hydantoin rings of the already given formula (lV-l) or (IV-2).

The sum of m I in the foregoing formula (l-3a) or (l3b) is preferably 2 to 4, particularly 2. In the aforesaid type 1 process, the glycine derivatives of which r is 2 may be concurrently used with no more than 40 mol "/0 thereof, particularly no more than 20% thereof, of another glycine derivatives of which r is 3, with advantage. Likewise, also in the type 2 and type 3 processes, the first component of which (m-H) is 1 can be concurrently used with no more than 40 mol 7c, particularly 20 mol thereof of another glycine derivatives of which (m l) is 3, to form the hydantoin ringcontaining polymers with advantage.

In the type 3 process using the polyfunctional glycine derivatives of the formula (1-3a) or (l-3b) containing the reactive groups other than primary amino group (i.e., B-Z, B-3, or 8-4) and glycine residues (Ga) or (Gb). particularly the below-specified practices of types 3-1 and 3-2 are preferred.

[TYPE 3-1] 1. The glycine derivatives of the formula (1-8) or (1-9) below,

in which R,, R R Y, and X have the already given definitions,

2. at least one primary amino group-containing polyfunctional compound selected from the group consisting of diamine of the formula (ll-la) below,

H N R NH (ll-la) in which R is a divalent organic group, and aminohydroxyl compound of the formula (II-2a),

HO R NH- (ll-2a) in which R 0 has the same definition'as that given as to the formula (ll-la) above, and

3. diaryl carbonate of the formula (III), in which 4) and have the already given definitions,

4. are mutually reacted 5. to form substantially linear hydantoin ringcontaining copolymer.

1. The glycine derivatives of the formula (1-10) or (1-1 1) below, I

in which R R R and X have the already given definitions, or I (l-ll) YOOC R NH R and X have the already given defi- (ll-3a) in which, Y and R have the already given definitions, and

3. diaryl carbonate of the formula (111),

O -o c o (111) in which (I) and have the already given definitions,

4. are mutually reacted,

5, to form substantially linear hydantoin ringcontaining copolymer.

The process of type 3 (inclusive of the above types 3-1 and 32) according to the invention is characterized in that the polyfunctional glycine derivatives (1-3a) or (1-3b) contain, besides at least one glycine residue (Ga) or (Gb), at least one reactive group (B') selected from the group as specified as to the formula (I-3a) or (I-3b):

a. hydroxyl group b. carboxyl group or ester groups thereof, and

c. carboxylic' anhydride group or functional derivative groups thereof.

Accordingly, in the type 3 process it is necessary to use at least one primary amino group-containing polyfunctional compound (11) besides the glycine derivatives (I-3a) or (1-3b) and diaryl carbonate. As such amino groupcontaining polyfunctional compound (11), the compound which contains i. at least two primary amino groups, or

ii. at least'one primary amino group and at least one functional group (E) which is not primary amino group and is reactable with the reactive group (B') in the formula (I-3a) or (1-3b) is used.

Preferred examples of the functional group (E) include:

(E-l) hydroxy group (-OH),

(E-2) carboxyl group or ester groups thereof covered by the formula, YOOC (Y standing for hydrogen atom or a monovalent hydrocarbon residue) and (E-3) carboxylic anhydride group bonded with two adjacent carbon atoms, or its functional derivative groups. (E-l) or (E-2), i.e., hydroxyl group, carboxyl group, and ester groups thereof are particularly preferred.

In such type 3 process of the invention, the diaryl carbonate not only reacts with the glycine residue (Ga) or (Gb) in the polyfunctional glycine derivatives (l-3a) or (l-3b), and the primary amino group in the primary amino group-containing polyfunctional compound (11-1, "-2, ll3, Il-la), or ll-2a) to form the hydantoin ring, but also reacts with the carboxyl group or ester group thereof in the glycine derivatives (l-3a) or (l-3b) and/or the primary amino group-containing polyfunctional compound (ll-3 or ll-3a) to form highly active aryl ester (OOC or 'OOC). Again, presumably the diary] carbonate (III) also reacts with the primary amino group (-NH. in the primary amino groupcontaining polyfunctional compound (ll-1, 11-2, or "-3), to form arylurethane which exhibits higher reactivity than primary amino group, with, for example, carboxyl group.

Thus according to the type 3 process, for example the carboxyl groups or ester groups thereof in the glycine derivatives (l-3a) or (l-3b) and/or primary amino group-containing polyfunctional compound (ll-l, "-2, or "-3) exhibit increased activity to accelerate the formation of carbamide bond (CONH) or carbester bond v O I ll --CO- through the reaction with primary amino groups or hydroxy group. Simultaneously, the reactivity of primary amino groups is similarly increased by the formation of the arylurethane, consequently further accelerating the formation of carbamide bond (CONH) with advantage.

If the diaryl carbonate (Ill) is added to the reaction system in excess of the quantity required for the formation of the hydantoin ring, and also if the primary amino groups present in the system are more than required for the hydantoin ring formation, the if the diaryl carbonate reacts with the surplus primary amino and urethane bonds (Mia) Whereas, when the glycine derivatives (l-3a) or (1-38) and/or the primary amino group containing polyfunctional compound (ll) contain a carboxylic anhydride group or functional derivative groups thereof, the reaction of such groups with primary amino groups progresses very smoothly to form carbimide bonds, and therefore it is unnecessary to use excessive diaryl carbonate (III) to accelerate the reaction. However, in that case the diaryl carbonate may also be utilized as a dehydrating agent of the water (H O) by-produced with the formation of the carbimide bond.

Accordingly, in practicing the type 3 process, the quantity of the diaryl carbonate (III) to be employed is preferably determined by taking such action of the diaryl carbonate (Ill) into consideration. For example, when it is intended to form a hydantoin ring-containing polymer through the hydantoin ring formation as well as carbamide bond (CONH) or carbester bond (COO), advantageously the polymerization reaction is advanced by using a mol number of the diaryl carbonate (III) which is at least equalling with the total mol number of glycine residues plus carboxyl groups participating in the formation of the ring and bond.

As already mentioned, the diaryl carbonate reacts with primary amino groups to form arylurethane. The arylurethane furthermore can react with the carboxylic anhydride group or functional derivative groups thereof, to form carbimide bond -N co Also the diaryl carbonate can form a carbonate bond Other types of copolymerization As mentioned above through the type 3 process of this invention, very wide varieties of hydantoin ringcontaining polymers which contain not only hydantoin rings but also at least one of such bonds as carbamide-, carbester-, carbimide-, earbonate-, urea-, and urethane-bonds can be prepared. Obviously, such a polymer can contain two or more types of such bonds if desired, which will be hereinafter referred to as the bond (a). According to the invention, furthermore, it is also possible to newly introduce into the product polymers at least one type of bond (at) selected from the group consisting of carbamide, carbester, carbimide, carbonate, urea, and urethane bonds, or to increase the number of such bonds (at), by applying the below-specified type 4 practice, not only to the type 3 process but also to the type 1 and type 2 processes. It should be obvious then, that upon introduction of such bond or bonds it also becomes possible to introduce (or copolymerize) new segments (or monomers) into, or with, the polymers.

According to the type 4 process,

1. either the polyfunctional glycine derivatives (1, or I-2a) and the diary] carbonate (III) are mutually reacted, or I g the polyfunctional glycine derivatives (I, or I-2a,

l-3a, or l-3b), the primary amino groupcontaining polyfunctional compound (II, or "-1 11-2, or 11-3 and the diary] carbonate are mutually reacted,

2. to form the polymers containing, in their main chains divalent hydantoin rings (lV-l or IV-2), such process covering all of the aforesaid types 1, 2, and 3 variations) 3. in which at an optional stage but before completion of the polymerization reaction, at least one polyfunctional compound (V) containing 2 to 6 functional moieties selected from the group consisting of a. carboxyl group of the formula VOOC (Y standing for hydrogen atom or a monovalent hydrocarbon residue), and ester groups thereof, b. carboxylic anhydride group bonding with the two adjacent carbon atoms, and the functional derivative groups thereof, and

c. hydroxyl group is added to the polymerization reaction system to be copolymerized. Thus the copolymers containing both the divalent hydantoin rings and also at least one type of the aforespecified bond ((1) in their main chains can be obtained.

As such polyfunctional compound (V), particularly those containing two to four functional groups of the specified type or types, inter alia, two functional groups, are suitable.

Thus, particularly the difunctional compound of the formula (V-l) below,

D Q E in which Q is a divalent organic group, D is at least one reactive moiety selected from the group consisting of a. carboxyl group of the formula YOOC (Y standing for hydrogen atom or a monovalent hydrocarbon residue) and derivative groups thereof, b. carboXylic anhydride group bonding with the two adjacent carbon atoms in the divalent organic group (Q'), and functional derivative groups thereof, and

E is at least one type of moiety selected from the group consisting of the above (a) carboxyl group and functional derivative groups thereof, (b) carboxylic anhydride group and functional derivative groups thereof, and (c) hydroxyl group (OH) is used with favorable results.

According to the invention, the polymers containing hydantoin rings and the bond (at) of still greater scope and varieties than those obtainable with the type 3 process can be prepared by applying the copolymerization process of above type 4.

Such type 4 process can be preferably performed by 30 practicing the already described processes of types 1-1, 3-1, and 3-2, particularly 3-1 and 3-2, in the concurrent presence of at least one difunctional compound (V-Z) selected from thegroup consisting of:

i. organic dicarboxylic acid and functional derivatives thereof,

ii. organic tricarboxylic mono-anhydride and functional derivatives thereof,

iii. organic tetracarboxylic di-anhydride and functional derivatives thereof iv. organic hydroxy carboxylic acid and functional derivatives thereof, and

v. organic monohydroxydicarboxylic anhydride and functional derivatives thereof.

So far the formation of hydantoin ring-containing polymers according to the invention has been described as to:

1. the process of reacting the functional glycine derivatives l) with diaryl carbonate (I11),

2. the process of reacting the functional glycine derivatives (I).with primary amino group-containing polyfunctional compound (ll) and diaryl carbonate (III), and 3. the modification of above process (1) or (2) in which another functional compound (V) is also added and copolymerized.

According to the invention, it is also possible to make various polymers containing hydantoin rings in their main chains similar to the products the above processes, by first forming a hydantoin ring-containing compound which also contains at least two reactive groups (B) which may be any of (8-1 (8-2), (8-3), and (B4) explained as to formula (I), or derivatives thereof having the aforesaid ary] ester (OOC-) or 6 arylurethane groups at the termini, through the processes of (1) and (2) above (for example, already described type 1, 2, and 3 processes); and then reacting the same with the polyfunctional compound (V).

According to the invention, extremely versatile polymers can be obtained through the so far described practices, for example, those of very high hydantoin ring segment concentration such as polyhydantoin obtained through the above type 1-1 or type 2-! process, as well as the eopolymers of low hydantoin ring concentration formed through the application of type 4 process. Whereas, in order for the hydantoin rings to affect the polymer properties with their advantageous characteristics such as high thermal stability and good solubility to any significant degree, it is preferred that the ratio of the hydantoin rings in the total groups bonded with the polymer main chain should be above a certain critical value.

Thus, the polymers in which the hydantoin ring bond occupies at least mol preferably 25 mol inter alia, at least 40 mol 7a, of the total bonds present in the polymer inclusive of the hydantoin ring bonds, are advantageous and desirable.

Hereinafter each of the components to participate in the reaction according to the invention will be described in further details.

Polyfunetional glycine derivatives (l):

As already specified, the polyfunctional glycine derivatives (l) to be employed in this invention are expressed by the formula (I) below:

in which Z is an (a b) valent organic group,

0 is a positive integer of l to 6,

I2 is a positive integer of O to 5, the sum of (u,+ 12) being a positive integer of 2 to 6, and

A and B each has the already given definitions.

The A in the above polyfunctional glycine derivatives (I) is a glycine residue (Ga) or (Gb) of the formula below:

HN-C-C 1 O c-cf I X 1TH 3 in which X has the same to that defined as meaning as the formula (G), and

R R and R have the same definitions as in formulae l-la and l-2a.

Again, the B in the polyfunctional glycine derivatives (1) denotes at least one reactive moiety selected from the group consisting of:

(B-l) primary amino group (NH (B-2) hydroxyl group (HO-) (B-3) YOOC (Y standing for hydrogen atom or a monovalent hydrocarbon residue) and f (8-4) carboxylic anhydride group bonding with the two adjacent carbon atoms in the organic group (Z) and functional derivative groups thereof.

When the Y in the above group (B-3) is a monovalent hydrocarbon residue, it is suitably selected from aliphatic, alicyclic, and aromatic hydrocarbon groups of l to 20 carbon atoms, particularly 1 to 10 carbon atoms. More specifically, methyl, ethyl, phenyl, toluyl and benzyl groups are particularly preferred.

For an easier understanding, the polyfunctional glycine derivatives (I) can be classified into the following three groups.

1. polyglycine derivatives containing 2 to 6 glycine residues (Ga) or (Gb) but containing no reactive group (B) (b 0) which belong to the formula (l-la) or (I-lb).

2. aminoglycine derivatives containing at least one glycine residue (Ga) or (Gb) and at least one primary amino group (B-l which belong to the formula (l-2a) or (l-2b), and

3. polyfunctional glycine derivatives containing at least one glycine residue (Ga) or (Gb) and at least one reactive group selected from the aforesaid groups (3-2), (8-3), and (8-4), which belong to the formula (l-3a) or (l-3b).

Each of the foregoing three groups will be explained in further detail below.

1. Polyglycine derivatives of the formula (l-la) or (l-lb) below:

3. Polyfunetional glycine derivatives of the formula (I-3a) or (l-3b) below:

In all of the above formulae. R R R X, R, r, m. l, B, and Rg have the same. definitions as previously given.

Hereinafter the glycine residue (G present in the above polyfunctional glycine derivatives l to (3) will be explained. i

In the glycine residue (Ga) o'r (Gb), R R and R may be the same or different, each denoting hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include aliphatic groups of l to 20 carbons such as methyl; ethyl, propyl, and butyl groups; alicyclic groups of 3 to 20 carbons such as cyclohexyl,

etc.; and aromatlc groups of 6 to 20 carbons such as phenyl, benzyl, toluyl, and naphthyl groups. The, preferred R,, R and R are hydrogen atom and methyl, ethyl, phenyl, and beniyl groups, particularly hydrogen atom, methyl and ethyl groups.

Also as already mentioned, the X in the glycine residue (G) denotes OR, SR', NHR, or N(R') (R' standing for hydrogen atomor a monovalent organic group), and as such monovalent organicgroup, for example, aliphatic, alicyclic, and aromatic. hydrocarbon groups of not more than 20 carbon atoms may be mentioned, the preferred being methyl, ethyl, phenyl, and benzyl groups. Preferred specific examples of x include OH, OCH;,, oc H SH, -NH NHCH N(CH etc. As the X, particularly those of OR type among the above-named are preferred.

In the polyfunctional glycine derivatives (l), the Z- in the formula (I) isan (a b) valent organic group. Morcspecifically, such Z is equivalent to R in the foregoing formula (I-la) or (I-lb) (which however is referred to as an r-valent organic group); and also is equivalent to Rg in the formulae (I Za), (I-2b)',' (I-3a) and (I-3b) (which is said to be an (I m)-valent organic group).

Such Z, R, or R,,, which are respectively (a b)- valent, r-valent, or (I m)-valent organic groups, can be any of, for example, saturated or unsaturated hydrocarbon residues of 1 to 30 carbons. The hydrocarbon residues also may be aliphatic, alicyclic, aromatic, or. hetercyclic groups. The hydrocarbon residues may also contain at least one of such elements as oxygen, nitrogen, sulfur, phosphorus, silicon and halogens. The bonds of those hydrocarbon residues are bonded with the carbon atoms.

Specific examples of such hydrocarbon residues (Z, R, or R are given below,:

i. saturated or unsaturated aliphatic hydrocarbons such as CH CH CH CH CH CH CH CH CI-I CH-CH CH CH CH CH CH CH-CH =Cl-I and CH;,(CH CH;,, etc.; I i

ii. alicyclic hydro carbons such as on 5 @414 CH2,

22 O, and @SO etc.;

iii. aromatic hydrocarbons such as I i in which M is selected from the group consisting of -O, lower alkylenes of l to 4'carbons,"NHCO-, 2

etc., K being a monovalent organic group); and iv. heterocyclic compound such as etc.

The foregoing hydrocarbon residues of (i) through (iv) may contain substitutent groups which are inert to the subject reaction, such as halogen atoms, e.g., chlorine, bromine, and fluorine; nitro group, and lower alkoxy groups such as methoxy and ethoxy.

The above specific examples of hydrocarbon residues are given only by way of illustration, and should never be construed to limit the scope of this invention in any sense.

As already mentioned, the polyfunctional glycine derivatives (I) employed in this invention are expressed by the formula (8),, Z (AM, in which it is desirable that A and B are not bonded with the same or two adjacent carbons of the gruop 2., because if the reactive group B atom bonded with the same carbon atoms with the glycine residue (G), or with the carbon atom adjacent to that on which the glycine residue (6) is bonded, they are apt to togethenform cyclic groups by the action of diaryl carbonate (III) as later described, to interfere with the intended hydantoin ring groupforming reaction.

Hereinafter exemplary polyfunctional glycine derivatives (I) to be employed in this invention are shown by their structural formulae.

1. polyglycine derivatives belonging to the formula (I-la) or (1- lb):

E is at least one reactive moiety (E) selected from the group consisting of: I (E-l hydroxyl group (HO), (ii-2) YOOC- (Y having the same meaning previously given). and (E-3) carboxylic anhydride group bonding with the two adjacent carbon atoms of the organic group (W), and functional derivative groups thereof.

The W in the above may be any one or combination of saturated or unsaturated aliphatic, alicyclic, aromatic, or hetero cyclic groups of 2 to 30 carbons, which may contain at least one hetero atom such as oxygen, nitrogen, halogens, sulfur, phosphorus, and silicon, etc.

Specific examples of W correspond to those given as the preferred specific examples of .Z in the polyfunctional glycine derivatives (1).

In the reactive moieties which can serve as E, specific examples ofY in the group (E-2), and of the functional derivative groups of carboxylic anhydride in (15-3) are similar to those given as to Y of (B-3 and functional derivative groups of (8-4), respectively. Incidentally, when two YOOC- moieties are bonded respectively with two adjacent carbon atoms, such E is regarded as a functional derivative group of carboxylic anhydride group covered by the definition of (E-3), rather than (E-2), like the similar case in formula (l).

in the selection of specific primary amino groupcontaining polyfunctional compound (ll) for practicing the present invention according to the foregoing explanations, preferably the following conditions are further taken into consideration.

NH JZMD oxazolidone ring or cyclic carbonate which is objectionable for the purpose of this invention.

Again, even if they are bonded with two carbon atoms spaced by no less than three atoms, such a compound which is still apt to form stable intramolecular cyclic compound through the reaction with diaryl carbonate, as 1,8-naphthylenediamine, for example, is unsuitable for the purpose of this invention.

Exemplary specific examples of the primary amino group-containing polyfunctional compounds are as follows. i. When p 0, q 2 2, Le, the compounds of the formulae (II-l) and (II-1a):

Tctramcthylene diamine Hexamethylenediamine Dodecamcthylenediamine 1,4-Diamino-trans-butene (2) Cyclohexancl ,4-bis( methylene amine) 4,4'-Methylene-bis-cyclohexylarnine 3,9-Bis( B-aminopropyl )-2,4.8. l0- tetroxaspiro [5,5] undecane m-Phenylenediaminc p- Phcnylcncdiaminc 4-Chloro-m-phcnylencdiaminc 2-Nitro-p-phenylenediaminc 4Mcthoxy-ni-phenyleiiediamine ii. When p =1 and q= l:

(ii-oz). When E is HO (ll-2a):

ii-B. When E is YOOC (ll-3A) p-Aminophcnol m-Aminophcnol S-Amino-fimaphthol 4-Amino-4'-hydroxydiphcnylcthcr p- Hydroxyhenzylamine 4-Hydroxy eyclohexylamine l,5Pcntanulamine p-Aminohcnzoic acid m-Aminohenxoic acid Methyl p-aminohenzoatc Ethyl m-aminohenzoalc NH: Allyl p-aminobcnzoatc Phenyl p-aminohcnzoatc Holl O N H 4-( 4-Aminophcnoxy )bcnzoic acid HOC-(CHgr NH e-Aminu caproic acid ii--y. When E is (E-3):

Tranexamic acid rat X 4-Aminophthalic anhydride HO'Q'O NH2 2.4-Diamino-4hydroxydiphenylcthcr NH Fl) r) QCQCOH S-Aminoisophthalic uCld NH: 1? HOC 0 \NH. 4(2,4-Diaminophcnyloxy) benioic acid, NHL,

The above-named glycine derivatives (l) and primary amino group containing polyfunctional compound (II furthermore, may be used in the form of ammonium salts, such as carbonate, hydrochloride, sulfate, phosphate, and sulfonate. In such a case, it is necessary that an acid acceptor such as tertiary amine is separately used to cause regeneration of the amino groups at the time of reaction except in the casewherein the salt is easily dissociated or decomposed under heating, like carbonate.

Also when the compounds (I), (II), and later described polyfunetional compound (V) contain carboxyl groups and phenolic hydroxyl groups, a part or all of which may be converted to carboxylate, phenolat e, or the like of, for example, tertiary amine salt, alkali metal salt, etc., before the compounds are fed to the reaction system.

Diaryl carbonate (Ill) In the general formula (III) to cover the diaryl carbonate useful for the invention (1) (1) may be same or different, each denoting a monovalent aromatic group which is subject to no other limitations. Because after the reaction the formed OH or OH does not enter into the object product; diaryl carbonates of lower molecular weights, and which are stable themselves as well as in the forms of OH and rbOH are preferred. The reactivity of diaryl carbonate is generally higher when the (b and 15 provide OH and S'OH of stronger acidity. Accordingly, depending on the types of the compounds (I) and (II) to be employed, diaryl carbonate of especially high activity may be selected.

As normally preferred diaryl carbonate, diphenyl carbonate, ditoluyl carbonate, phenyl toluyl carbonate, bis( nitrophenyl carbonate, bis( ehlorophenyl) carbonate, dinaphthyl carbonate, and dibiphenyl carbonate, etc., can be named. Particularly diphenyl carbonate is cheap and normally used with best preference.

According to the invention, diaryl carbonate is used primarily in stoichiometric amount or in a slightly excessive amount with favorable results, but when diaryl carbonate decomposing reaction or side-reaction takes place under certain reaction conditions, excessive amount to offset the expected loss is preferably used.

Polyfunctional compound (V) The polyfunctional compound (V) to be used as the copolymerizable component according to the invention can be expressed by the general formula (V) below:

Q E v in which Q is a j'valent organic group, -j. is a positive integer of 2 to 6, and

E has the already defined signification.

Q is selected, for example, from saturated or unsaturated aliphatic, alieyclic, aromatic, or heterocyclic groups of 2 to 30 carbons, which may be used in combi-' nation of one or more. The organic group may contain at least one hetero atom such as oxygen, nitrogen, halogen, sulfur, phosphorus, silicon, etc.

Specific examples of such Q correspond to the suitable specific examples of Z in the general formula (I) denoting the polyfunctional glycine derivatives.

In the selection of specific compound (V) according to the abovegiven conditions, it is desirable to also take the following matters into consideration.

That is, a compound containing a pair of hydroxyl groups spaced by 2 or 3 carbon atoms, which forms a stable cyclic carbonate through the reaction with diaryl carbonate, e.g., ethylene glycol, catechol, l,8-dihydroxynaphthalene, etc. in the copolymerization system in the concurrent presence of diaryl carbonate should be avoided. Such a compound can be used with no detrimental effect, however, for the chain extending reaction with, for example, aryl ester, at the polymer terminals, after all the diaryl carbonate is consumed.

Hereinafter the specific examples of the polyfunctionaleompounds (V) to be used as the copolymerizing component will be explained.

l. Difunctional compound (j 2):

i. dihydroxy compound aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, and l,6-hexanediol; alicyclic glycols such as ao on,

phthalic, terephthalic, 1,5-, 2,6-, or 2,7- naphthalenedicarboxylic, 3 ,3 or 4,4- diphenyldicarboxylic acids, 3,3'-, or 4,4- diphenylsulfonedicarboxylic, 3,3 or 4,4-

diphenyletherdicarboxylic, iso-cinchomeronic and dinicotinic acids.

Furthermore, dicarboxylic acids containing imide groups of the formulae Va, VB, and Vc below may also be used.

(in the above formulae, R denotes a trivalent organic group, R is a divalent organic group, and R denotes a tetravalent organic group).

Those dicarboxylic acids are similarly usable in the forms of lower alkyl esters or aryl esters. The aromatic dicarboxylic acids may contain on their aromatic rings such inert substitutents as alkyl group, alkoxy group,

and halogen atoms, etc.

iv. tricarboxylic mono-anhydridcs and tetracarboxylic di-anhydrides For example, tricarboxylic monoanhydrides such as trimellitic monoanhydride, 3,3 ,4 l -diphenyltricarboxylic anhydride, 3 ,3 ,4- diphenylsulfone tricarboxylic anhydride, 2,3,6-

naphthalene tricarboxylic anhydride, etc.; and tetracarboxylic di-anhydrides such as butane tctracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 3,3, 4,4- diphenylsulfone tetracarboxylic dianhydride, 2, 3, 6, 7-naphthalenc tetracarboxylic dianhydride, and l, 4, 5, S-naphthalene tetracarboxylic dianhydride, etc., are convenientlyv used. Again such tricarboxylic monoanhydride and tetracarboxylic dianhydride of which acid anhydride groups are ring-closed upon hydrolysis or esterified with lower alcohol can be used with equivalent effect. 2. Polyfunctional compound j 3) Polyhydroxy compound such as glycerine, pentaerylthritol, trimethylolpropane, phenoxy resin, Novolak resin, tris-hydroxyethylisocyanurate, etc.; polycarboxylic acids such as trimesic acid, 1, 3, o-naphthalene tricarboxylic acid, 1, 3, 5, 7-naphthalene tetracarboxylie acid, etc., and their lower alkyl esters and aryl esters can suitably used.

Solvent (VI) The polymers obtained according to the invention generally have high melting points, and therefore in the majority of the cases the reaction can be performed more easily in the. concurrent presence of organic solvent, which allows easier controlling of the reaction. Addition of reaction medium, however, is not always essential, becauseduring the initial stage the diaryl carbonate which is normally liquid under the reaction temperatures, and after the middle stage the phenol byproduced from the participation of the diaiyl carbonate in the object reaction, may serve as the reaction medium, respectively.

When other solvent is added, it should be substantially inert to the reaction of the subject process, have a boiling point not lower than C, preferably C. or above, and preferably can dissolve, or at least sufficiently swell, the starting materials and intermediate polymers to maintain their activities.

As the solvents meeting the foregoing conditions, aprotic polar solvents such as N-methylpyrrolidone,

tetramethylcnesulfone, dimethylacetamide, dimcthylformamide, and nitrobenzene, are suitably employed. Also phenolic solvents such as crcsol, phenol. xylenol, etc., can be used with favorable results.

Particularly the phenolic solvent is of the same group with the phenols by-produced from the polymerization reaction and widely used in the making of wire enamel, etc. Thus the use of phenols as the solvent is very advantageous especially when the product is to be used as wire enamel, in which the by-product of the reaction can be used as solvent as it is. It is known, however, that normally the by-product from the polyeondensation reaction should be removed from the system if at all possible, to assist the smooth progress of the polyeondensation according to the theory of equilibrium. Thus when the subject reaction is to be performed in a phenolic solvent. the reaction conditions must be carefully selected to offset the handicap of effecting the reaction in the by product.

The amount of the solvent can be suitably dcter-- mined, depending on the type of object product, reaction conditions, etc. The concentration of the solvent need not be constant throughout the reaction, but can be suitably adjusted by such known means as concentration, dilution, etc., normally within the range as will make the polymer concentration in the system 95 to by weight.

Catalyst (VII) According to the present invention, normally the reaction can smoothly progress in the absence of catalyst to produce the object product. However, in certain cases catalyst for accelerating the reaction can be used if desired.

Examples of usable catalyst include oxides, hydroxides, alcoholates, chlorides, and-organic compounds of such metals as alkali metals, alkaline earth metals, tin, lead, titanium, cobalt, nickel, iron, manganese, antimony, and aluminum, etc.; tertiary amine; and quaternary ammonium base. As more specific examples, calcium oxide, magnesium oxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium ethylate, triethylamine, triethylammonium hydroxide, butyl titanatc, magnesium chloride, dibutyltin dilaurate, lead acetate, zinc acetate, etc., can be named. Such a catalyst is normally used within the range of approximately 0.05 5 mol to starting materials.

Polymerizations conditions The subject process is performed by reacting under heating each predetermined amount of the polyfunctional glycine derivatives (I) with diary] carbonate (Ill), and if necessary also the primary amino groupcontaining polyfunctional compound (II), in the optional presence of polyfunctional compound (V), solvent (VI), and catalyst (VII).

The foregoing compounds (I), (II), (III), (V), (VI), and (VII) may be added to the reaction system all at once in the beginning of the reaction. Depending on the types of combination of the monomers and object polymer, however, they maybe added in suitable sequence or in divided portions with advantage.

For example, in certain cases by first reacting (l) with (III), or (I), (II), and (III), to form hydrantoincontaining intermediate condensation product having such functional groups hydantoin aryl ester, arylurethane, aryl carbonate, or amino groups at the termini, and then adding (V) which is reactable with the termi- 36 nal reactive groups, the polymerization may be completed with more favorable results.

On the contrary, in other cases it may be preferred to react (V) alone, or (V) with (II), or (V) with (l), in advance, to form intermediate condensation products containing primary amino groups and/or glycine residue at the termini, and then react the same with (I) and/or (II) and (III) to effect chain extension through the reaction including the hydantoin ring-forming reaction, thereby completing the polymerization. Still in other cases (II) and/or (V) are reacted with (III) in advance to form intermediate condensation product, and then (I) and if necessary (III) are added to the system to form the hydantoin rings.

If the (I), (II), or (V) contains the acid anhydride group of (E-3 normally the imide bond-forming reaction of the anhydride groups with primary amino groups via the form of amide acid takes place before the hydantoin rings are formed. Therefore, it is preferred to cause first the formation of imide bond, re-

'move the by-produced water, and then to add (III) to effect the hydantoin ring formation.

As already mentioned, it is not essential to add a fixed amount of solvent at the beginning of the reaction. In certan cases it may be preferred to start the reaction in the absence, or in the presence of a very minor amount, of a solvent, and as the polymerization progresses the solvent of the amount suitable for, for example, facilitating the agitation, is gradually added to the system. Conversely, it.may be a preferred practice to gradually distill the solvent off from the system under concentration, to raise the reaction temperature.

Furthermore, catalyst can be added not only from the start, but also at an optional stage or stages of the polymerization if necessary, to achieve the optimum results.

In the preparation of curable polymers of crosslinked structure, normally fusible and soluble prepolymers are first formed, which are later cross-linked during or after the molding by the post-curing reaction. In that case, if the reaction excessively advances in the stage of making prepolymer, gelated portions are formed to impair the effect of the invention. Accordingly, it is preferred to perform the former reaction in the absence of catalyst, or using a very minor amount of catalyst, and to add a sufficient amount of the catalyst to the post-curing system to improve the curing efficieney.

The polyeondensation reaction of the invention is normally performed at 400C, preferably from 100 to 300C, particularly l50 250C., while the temperature is preferably raised gradually from the initial low temperature, in order to effect smooth progress of the polymerization avoiding side-reactions.

The reaction time is variable depending on other reaction conditions and required type, degree of polymerization, and properties of the polymers, normally within the range of approximately 0.5 to 30 hours.

The side-products of the polyeondensation reaction such as water, alcohol, carbon dioxide, etc. may cause objectionable side-reactions such as decomposition of diaryl carbonate, if present in the reaction system. Therefore, they should preferably be quickly removed out of the system by such means as distillation. In certain cases, it may also be preferred to effect the reac tion while eliminating the side-produced phenols ((bOH, 'OH) as formed.

The polycondcnsation reaction of the invention is normally practiced under atmospheric pressure, but elevated or reduced pressures may be employed if desired. Particularly when the reaction is necessarily performed at the temperature not lower than the boiling.

point of the solvent and/or monomers, elevated pressures are preferably employed. Whereas, when the p01: ymer of required degree of polymerization cannot be obtained unless the side-products are sufficiently removed from the system due to the theory of equilibrium in polycondensation reaction, the distillation of side-products can be facilitated by performing the reaction under a reduced pressure.

In order to avoid damage of the starting materials and functional groups by oxidation, etc., the reaction is preferably performed in an inert atmosphere such as of nitrogen, argon, etc.

It is a generally preferred practice 'to use a reactor equipped with a fractionationtype reflux condenser for convenient distillation of side-products as abovementioned, as well as for refluxing the solvent.

The polycondcnsation reaction of the invention may be completed in the reactor, or may be suspended at the intermediate stage where the prepolymer is formed, and later completed by the heat-treatment for shaping the prepolymer into coating, film, laminates, orother bulky shaped products. Particularly with the aforesaid cross-linked polymers, the latter practice is preferred.

The temperature condition of such heat treatment differs depending on the type of polymer, treating time and the manner of heating, but normally that of 150 450C, preferably 200 400C. is selected.

When the polymer is thus obtained in the form of a homogeneous solution at the end of reaction, it can be used as an impregnating solution, varnishaand adhesive, etc., either as it is or after suitable processing such as dilution or addition of additives. Again the polymer may be once isolated by known means such as reprecipitation, filtration, drying, etc. to be used as a material for melt-molding or again dissolved in suitable solvent to serve as an impregnating solution molding. The latter procedures are also applicable to the case wherein the polymer is obtained as precipitate. In ac-. tual practice the polymers may be blended with other resin or added with suitable additives. I

As so far described, the polymerization conditions can be suitably selected depending on the typeof starting materials, object polymer, and the intended utility of the product. More specific optimum conditions for individual practice can be easily empirically determined by the expert of the art. I

The above-mentioned polymerization conditions may be further modified by application of, or combination with, other accepted practices.

Confirmation of polymer structure 'The structures of the polymers and intermediate products obtained through the subject process can be confirmed by such known means as infrared absorption spectrum, NMR spectrum, elementary analysis, etc. Particularly the formation of hydantoin rings can be traced by infrared absorption spectrum.

The degree of polymerization can be readily judged by measuring the polymers intrinsic viscosity. Non mally the polymer formed by the subject process has the intrinsic viscosity (1; inh.),- as'- measured with m-- 1 ymerization are achieved simultaneously, which is an cresol o'r N-methylpyrrolidone solution of 0.5 g/lOO ml concentration at 30C., within the range of 0.1 to 2.

The polyhydantoins obtained through the subject process, particularly aromatic polyhydantoins, exhibit excellent heat stability, electrical insulation, and mechanical properties, as well as high solubility, The polyhydantoins are thus soluble in a wide range of organic solvents, and consequently are easily processible, and suited for various utilities such as electrically insulative materials, machine parts, etc., in the forms of, for instance, coating such as wire enamel, adhesive, laminates, shaped products, film, fibers, etc. The polyhydantoins also exhibit excellent compatibility with other resins, and have similarly wide utilities in blended compositions.

According to the present invention, instead of the isocyanate compounds of which industrially usable types are severely limited as already mentioned, the corresponding amine compounds, which are the precursors of the former, are used to enable single-stage preparation of polyhydantoins. Thus wide varieties of polyhydantoins suited for various utilities can be industrially advantageously supplied.

Furthermore, as already stated, according to the invention it is possible to introduce hydantoin rings as co-' polymerizing component in the optional form and at an optional rat' the various polycondcnsation productssuch as polyimide, polyamide, polyester, polyesteramide, polyesterimide, polycarbonate, polyurethane, polyurea, etc. Such various polymers acquire practically very important and advantageous properties upon 'the introduction of hydantoin rings. For example, en-

tirely aromatic type polymers such as polyimide, polyamideimide, polyamide, polyester and polyesterimide, etc., are produced with higher solubilities in organic solvents while fully retaining their inherently high heat stability. Thus the modified polymers exhibit markedly improved processibility.

Again, polycarbonate and certain polyester, polyamide, and polyesteramide can be produced with markedly imporved heat stability, witout impairing their inherent processibility.

Incidentally, the diaryl carbonate employed for the hydantoinring formation according to the invention also participates in the formation of polycarbonate, polyurethane and polyurea bonds as an essential component, and concurrently accelerates the formation of amide bonds and ester bonds in the aforesaid polyamide, polyester, polyamidimide, polyesterimide, and polyesteramide, etc. According to the subject process, therefore, both the desired modification of products by introduction of hydantoin rings and acceleration of polimportant industrial advantage of the invention.

The phenols by-produced during the subject process may be utilized as the solvent of the polymer as they are, or, when recovered by, for example, distillation, they can be recycled into the diaryl carbonate-forming system, and thus never wasted.

The reaction of the subject invention in which the diaryl carbonate participates exhibits activity satisfactory for practical purpose, but the reaction progresses at a moderate rate, unlike the violent reactions such as that between the primary or secondary amino group in the glycine derivatives and isocyanate group, or that between primary amino group and carboxylic acid halide, which are difficult to control. 

1. A PROCESS FOR THE PREPARATION OFPOLYMERS CONTAINING DIVALENT HYDANTION RING GROUP OF THE FORMULA (IV) BELOW:
 1. POLYFUNCTIONAL GLYCINE DERIVATIVE (1) CONTAINING AT LEAST ONE GLYCINE RESIDUE (G), WHICH IS EXPRESSED BY THE FORMULA (1) BELOW
 2. AND WHEN THE GLYCINE DERIVATIVE (I) DOES NOT CONTAIN. THE PRIMARY AMINO GROUP (B-1), A POLYFUNCTIONAL COMPOUND (II) HAVING 2-6 FUNCTIONAL GROUPS (F) WHICH ARE REACTIVE WITH AT LEAST ONE OF THE SAID GROUPS (A) AND (B), WHEREIN THE COMPOUND (II) CONTAINS AT LEAST ONE PRIMARY AMINO GROUP AS THE FUNCTIONAL GROUP (F), WITH
 2. The process of claim 1 wherein the primary amino group-containing polyfunctional compound (II) is at least one polyfunctional compound selected from the group consisting of (II-1) polyamine (II-1) containing at least two primary amino groups, (II-2) aminohydroxyl compound (II-2) containing at least one primary amino group and at least one hydroxyl group, and (II-3) aminocarboxylic acid derivatives (II-3) containing at least one primary amino group and at least one carboxyl group or ester group expressed by the formula, YOOC-, wherein Y is a hydrogen atom or a monovalent hydrocarbon residue.
 2. and when the glycine derivative (I) does not contain the primary amino group (B-1), a polyfunctional compound (II) having 2 - 6 functional groups (F) which are reactive with at least one of the said groups (A) and (B), wherein the compound (II) contains at least one primary amino group as the functional group (F), with
 2. polyamide (II-1) of the formula, R''- NH2)S(II-1) wherein R'' is an S-valent organic group, and S is a positive integer of 2 to 6, and
 2. at least one primary amino group-containing polyfunctional compound selected from the group consisting of (II-1) polyamine (II-1) containing at least two primary amino groups, (II-2) aminohydroxyl compound (II-2) containing at least one primary amino group and at least one hydroxyl group and (II-3) amino carboxylic acid derivatives (II-3) containing at least one primary amino group and at least one group of the formula YOOC-wherein Y is a hydrogen atom or a monovalent hydrocarbon residue, with
 2. primary amino group-containing polyfunctional compound (II) selected from the group consisting of (II-1) polyamine (II-1) containing at least two primary amino groups (II-2) aminohydroxyl compound (II-2) containing at least one primary amino group and at least one hydroxyl group, and (II-3) amino carboxylic acid derivatives (II-3) containing at least one primary amino group and at least one group of the formula, YOOC-wherein Y is a hydrogen atom or a monovalent hydrocarbon residue
 2. at least one primary amino group-containing polyfunctional compound selected from the group consisting of diamine of the formula, H2N - R10 - NH2 (II-1a) wherein R10 is a divalent organic group, and aminohydroxyl compound of the formula HO - R10 - NH2 (II-2a) wherein R10 is as defined above, and the diaryl carbonate of the formula (III) wherein phi and phi '' have the previously given definitions.
 2. primary amino group-containing polyfunctional compound of the formula, YOOC - R10 - NH2(II-3a) or HO - R10 - NH2(II-2a) wherein Y has the previously given definition, and a divalent organic group and (3) the diaryl carbonate of the formula (III),
 3. diaryl carbonate of the formula (III)
 3. diaryl carbonate of the formula (III),
 3. a polyfunctional compound (V) containing at least two functional groups selected from the group consisting of a. carboxyl group and ester groups thereof of the formula YOOC-, Y standing for hydrogen atom or a monovalent hydrocarbon residue, b. carboxylic anhydride group
 3. diaryl carbonate of the formula (III),
 3. diaryl carbonate of the formula (III) below,
 3. The process according to claim 1 in which the said polymers containing hydantoin rings in their main chains have the intrinsic viscosities ( eta inh.) between 0.1 and 2, said viscosity being measured with the solution of 0.5 g of the sample polymer in 100 ml of m-cresol or N-methylpyrrolidone at 30*C.
 3. DIARYL CARBONATE OF THE FORMULA (III) BELOW,
 4. The process of claim 1 wherein the polyfunctional glycine derivative (I) is at least one polyfunctional compound selected from the group consisting of (I-1) polyfunctional compounds (I-1) containing at least two glycine residues (G), wherein b is zero and a is a positive integer of at least 2, (I-2) polyfunctional compounds (I-2) containing in their molecules at least one glycine residue (G) and at least one primary amino group wherein A is the glycine residue (G) and B is a primary amino group, and (I-3) polyfunctional comopunds (I-3) containing in their molecules at least one glycine residue (G) and at least one reactive moiety selected from the group consisting of a. hydroxyl group b. carboxyl group or ester groups thereof expressed by the formula, YOOC- wherein Y is a hydrogen atom or a monovalent hydrocarbon residue, and c. carboxylic anhydride group
 4. a polyfunctional compound (V) containing at least two functional groups selected from the group consisting of a. carboxyl group and ester groups thereof of the formula YOOC-, Y standing for hydrogen atom or a monovalent bhydrocarbon residue, b. carboxylic anhydride group
 5. The process of claim 1 wherein the polymers containing divalent hydantoin ring groups in their main chains, are expressed by the formual (IV-1) or (IV-2),
 6. The process of claim 1 wherein the polymers containing divalent hydantoin ring groups in their main chains are expressed by the formula (IV-1) or (IV-2),
 7. The process of claim 1 wherein the polymers containing divalent hydantoin ring groups in their main chains are expressed by the formula (IV-1)
 8. The process of claim 1 wherein the polymer coNtaining the divalent hydantoin ring groups are co-polymers containing divalent hydantoin ring-containing polymers of the formula (IV-1)
 9. The process of claim 1 wherein the polymer containing the divalent hydantoin ring groups are co-polymers containing divalent hydantoin ring-containing polymers of the formula (IV-1)
 10. The process for making hydantoin ring-containing polymers according to claim 1 which are substantially linear and which have the recurring structural unit of the formula (IV-3) or (IV-4) below,
 11. The process for making hydantoin ring-containing copolymers according to claim 10 which are substantially linear in which the reactants are reacted in the concurrent presence of a difunctional compound (V-1) of the formula, D - Q'' - E (V-1) in which W'' is a divalent organic group, D is at least one reactive group selected from the group consisting of a. carboxyl group or derivative groups thereof of the formula YOOC-, Y being hydrogen atom or a monovalent hydrocarbon residue, and, b. carboxylic anhydride group
 12. The process for making hydantoin ring-containing polymers according to claim 1 which are substantially linear and which are composed of the recurring structural unit of the formula (IV-5) or (IV-6) below
 13. The process for making hydantoin ring containing copolymers according to claim 12 which are substantially linear in which the reactants are reacted in the concurrent presence of a difunctional compound (V-1) of the formula, D - Q'' - E (V-1) in which Q'' is a divalent organic group, D is at least one reactive group selected from the group consisting of a. carboxyl group or derivative groups thereof of the formula YOOC-, Y being hydrogen atom or a monovalent hydrocarbon residue, and b. carboxylic anhydride group
 14. The process for making hydantoin ring-containing copolymers according to claim 1 which are substantially linear, which comprises inter-reacting
 15. The process for making substantially linear, hydantoin ring-containing copolymers according to claim 14, in which the reactants are inter-reacted in the concurrent presence of at least one difunctional compound selected from the group consisting of i. organic dicarboxylic acid and functional derivatives thereof, ii. organic tricarboxylic mono-anhydride and functional derivatives thereof iii. organic tetracarboxylic dianhydride and functional derivatives thereof, iv. organic hydroxycarboxylic acid and functional derivatives thereof, and v. organic monohydroxy-dicarboxylic anhydride and functional derivatives thereof.
 16. The process for making hydantoin ring-containing copolymers according to claim 1 which are substantially linear which comprises inter-reacting
 17. The process for making substantially linear hydantoin ring-containing copolymers according to claim 16 in which the reactants are inter-reacted in the concurrent presence of at least one difunctional compound selected from the group consisting of i. organic dicarboxylic acid and functional derivatives thereof, ii. organic tricarboxylic mono-anhydride tricarboxylic functional derivatives othereof iii. organic tetracarboxylic dianhydride and functional derivatives thereof, iv. organic hydrocarboxylic acid and functional derivatives thereof, and v. organic monohydroxy-dicarboxylic anhydride and functional derivatives thereof.
 18. The process according to claim 1 in which the polymerization reaction is performed by heating the system to a temperature in the range of from 100* to 400*C. 